Surface-active products



United States Patent Ofi $38,024 Patented Apr. 30, 1968 3,380,924SURFACE-ACTIVE PRGDUCTS Bruno Werdeimann, Haan, Rhineland, Kari-HeinzWorms, Dusseldorf, Germany, and Bruno Blaser, deceased, late ofDusseldorf-Urdenbach, Germany, by Ida rllaser, nee Ban, administratrix,Dusseldorf-Urdenbach, Germany, assignors to Henlrel & Cie. G.m.b.H.,Dusseldorf-Holthausen, Germany No Drawing. Continuation-impart ofapplication Ser. No. 427,530, Dec. 29, 1964, which is acontinuation-in-part of appiieation Ser. No. 5,130, Jan. 28, 1960. Thisapplication 32a. 21, 1966, er. No. 523,012 Claims priority, applicationGermany, Feb. 6, 1959, H 35,571 2 Claims. (Cl. 252-117) ABSTRACT OF THEDISCLOSURE Detergent soaps stabilized against rancidity anddiscoloration by addition of 005-25 weight percent of a compound of theformula its sodium, potassium, ammonium or ethanolamine salts, wherein Ris a saturated aliphatic hydrocarbon having 1 to 11 carbon atoms orphenyl.

This application is a continuation-in-part of our copending applicationSer. No. 427,530, filed Dec. 29, 1964, now abandoned, which, in turn,had been a continuationin-part of our application Ser. No. 5,130, filedJan. 28, 1960, and now abandoned.

The invention relates to surface-active materials and their productionand, more particularly, to the increase in the stability of suchproducts.

Surface-active products are used in daily practice for a number ofpurposes, e.g., for the cleaning of all kinds of surfaces. Such productsare, e.g., soaps for cleansing of human and animal bodies and fortextiles, laundering agents, detergents and cleansing agents for metals.The surface-active materials are sold in the form of flakes, granules,powders, pastes, and as solutions, with or without additives.

It has been established that surface-active products frequently diminishin their quality and efiiciency upon storage, particularly by exposureto light. This is evidenced by rancidity, formation of spots,discoloration and changes in odor.

Attempts have been made at the prevention of these efiiciency decreasesby the addition of suitable stabilizers and of antioxidants to thesurface-active agents. Particularly in the case of soaps, alkali saltsof ethylene diamine tetraacetic acid and of nitrilo acetic acid havebeen proposed as such stabilizers. Alkyl benzene sulfonates tend tobecome rancid, and it has been suggested to add aryl biguanides andsimilar compounds thereto to prevent or decrease rancidity. It also hasbeen suggested to use monophosphonic acids for the stabilization ofsoap. However, none of the compounds named above have met with completesuccess since it is required that additives comply with a number ofconditions in order to be effective.

For instance, the additives must have neither color nor odor and mustnot react with heavy metals, which frequently are present as traces,under formation of colored compounds. Moreover, the additives must notbe volatile nor poisonous and must not react with the surface-activecompounds. Also, materials which are decomposed by alkalies cannot beused as additives. The additives must not have a deleterious action onthe foaming capabilities of the surface-active products. Furthermore, itis desirable that the additives are effective in small amounts and thatthey retain their action over a long period of time. Odorants, e.g.,perfumes added to soaps, must not be adversely affected by theadditives. Finally, especially in the case of toilet soaps which aremarketed in fairly large pieces, these must not embrittle under theaction of the additives. It now has been found that the requiredconditions for stabilization as named above are fulfilled by theaddition of compounds having the following Formula 1:

wherein R is an aliphatic hydrocarbon radical having 1 to 11 carbonatoms or a phenyl radical, or by the addition of their salts.

These compounds are produced by the reaction of phosphorous acid withcarboxylic acid anhydrides, carboxylic acid chlorides or mixtures ofthese anhydrides and chlorides in molar proportions of phosphorous acidto acylating agent of l:1.1-1:l.5 at temperatures ranging from roomtemperature to substantially 180 C. Suitable carboxylic acid anhydridesand chlorides are those of carboxylic acids having 2 to 12 carbon atomsin their molecules, such as acetic acid, propionic acid, butyric acid,valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonicacid, capric acid, undecylic acid, lauric acid and benzoic acid. Thesubstances can be added to the surface-active materials to be protectedin refined or also in crude state. In lieu of the free acids obtained bythe acylation, their alkali metal-, ammonium-, mono-, diandtriethanolamine salts can be used, obtained by neutralization with thecorresponding bases.

T he compounds thus obtained all contain 2 phosphorus atoms and have theFormula 1, wherein one carbon atom less is contained in the radicalshown as R than in the carboxylic acid used in the acylation.

The additives according to the invention have no surface-activeproperties of their own and are incorporated in the surface-activeproducts in solid form or in solution. The surface-active productsthemselves may be present in solid, molten or dissolved state during theincorporation. The soaps to which the stabilizers named are added arecommercial soaps, such as fine or toilet soaps, curd soaps, and softsoaps. The term soap, as is customary, denotes fatty acid sodium,potassium or ammonium salts or mixtures thereof. They may contain suchadditional ingredients as are commonly used for the purpose ofapplication, such as, e.g., alkalies, phosphates, silicates, glycerides,colorants, odorants and fillers. In order to attain the desired effect,merely small quantities of the additives according to the invention arerequired, namely 0.05 to 2.5 percent and, preferably, 0.2 to 1 percent.

The invention now will be further illustrated by means of the followingexamples describing the preparation of a number of storageable soaps anddemonstrating the effects. However, it should be understood that theseare given merely by way of explanation, not of limitation, and thatnumerous changes may be made in the details without departing from thespirit and the scope of the invention as hereinafter claimed.

Example 1 In Table 1 the results are listed, obtained with soapscontaining the additives named below. The left vertical column names thetest conditions. Horizontal columns 1 to 9 give the effects obtainedusing the same commercial 3,380,924. 3 4 soap in all tests in which thefollowing additives had droxide, carbonate or bicarbonate of the alkalimetals, been incorporated. ammonium or the mono-, dior triethanolarnine.The coumn No additive term neutralization is to be interpreted in such amanthat the acidic hydrogen is replaced by the corre- 2: 0.25 ght e-ce tof the tetrasodium salt net d f e t hylene dia ri i inote raace tic acid(this compound 5 sppndmg Canon totally m part The products tObfrequently is employed for the prevention of the detetimed a not i thePH g i i rioration of the quality of soap). e iz i y rfigen yhadcatlonWeen an y e exc ange 0 W0 y rogen a orns,

Column 3.0.25 weight percent of the disodium salt of 2 the PH is betweenand 6; y the exchange of three y hydroxy-Z-propanephosphonic acid.drooen the g pH is 9 to 10, and when all four hydrogen Column 4. 0.25Weight percent of the tetrasodium salt of atoms are replaced, the PH is11 to 12 a compound havmg Formula 2: It is to be noted that otherorganophosphorus compounds, such as l-one-l-phosphonic acid esters;ethanef f 1,2-diphosphonic acid; tetraethyl-l-hydroxyethane-l,l-di-HOPCIOII (2) phosphonic acid esters; tri-o-tolylphosphite;decyldihydrogen phosphate; or stearylaminophenylphosphonic acid esters;have either no stabilizing effect at all or at best Column 5: 0.45Weight percent of the di-(triethanolarnine) fig ig i efiect on soapunder the commons of salt of a compound havmg Formula 3: The superiorityof the additives according to the inven-. tion is not diminished when tothe soaps 10 to mg.

f (32m copper or iron ions are added per kilogram. Without the HOPCPOH(3) additives according to the invention, the presence of these e 11heavy metal ions leads to strong discoloration and change 5 in color.

TABLE 1.TYPE ADDITIVE IN SOAP Conditions of Investigation 1 2 3 Notexposed tolight Storedtiweeks Single light-yellow spots, fatty N 0effect Single light-yellow spots.

0 01. In light-exposure box 3 sunny days Yellow spots, rancid, tackySingle yellow spots,j atty odor 10 hours UV radiation Yelowedlk withdarker yellow N 0 discoloraticn,tatty odor spo s tac y. 144 hours C. inopen vessel Brown spots Diry-ivory color, slightly rancid Yellowed,rancid odor.

O 01. 144 hours 60 C. in airtight container Fewe sgots than above,slightly Light ivory color, no odor change" Yellowed, slightly rancidodor.

ranci 0 or.

Conditions of Investigation 4 5 6 Not exposed to light. Stored 6 weeksNo efiect No effect No en ct. In light-exposure box 3 sunny days Almostno discoloration, fatty odor 10 h rs UV radiation Unchanged in color andodor 144 hours 60 C. in open vessel Single ivory discolorations onSingle ivory discolorations on Single ivory discolorations on edgesslightly fatty odor. edges, slightly fatty odor. edges, slightly fattyodor. 144 hours 60 C. in airtight container Unchanged in odor and colorUnchanged in odor and color Unchanged in odor and color.

Conditions of Investigation 7 8 9 Not exposed to light. Stored 6 WeeksN0 e ect N0 effect No efieot In light-exposure box 3 sunny days 10 hoursUV radiation 144 hours 0 (1 i open ve l Single ivory discolorations onSingle ivory discolorations, sliglit- Ivory discoloration, slightlyfatty edges, slightly fatty odor. ly fatty odor. odor.

144 hours 60 C. in airtight container Unchanged in odor and colorUnchanged in odor and color Unchanged in odor and color.

Column 6: 0.6 weight percent of the tetra-(diethanolamine) Example 2salt of compound 4:

For the manufacture of an especially storageable toilet o o H 0 11 [j 1H 50 soap, percent fine sodium soap chips are entered in a HO I|)*(J:FOH (4) mixing machine with the usual proportions of superfat- H OHtening agents, titanium dioxide and perfume. Added there- Column 7: 0.25Weight percent of the diammonium alt to are 0.5 percent of the totalWeight of the tetrasodium of compound 5: 55 salt of a compound havingFormula 2. The soap is mixed 0 CSHU O With these components in the usualmanner, is extruded (5) and shaped.

HO OH OH Example 3 Column 8: 0.45 weight percent of the tetrapotassiumsalt 0 of compound 6: For the manufacture of a curd soap in a crutcher,one

proceeds as follows: To 3 tons settled sodium soap curd O C H9 0 ii ofapproximately 0.06 percent free alkali, calculated as HOI{-(I3 II) OH(6) NaOH, and 0.3 percent NaCl, 2 percent aqeous solution HO OH 01-1 5of the sodium salt of the compound named as Formula 2 Column 9: 0.3weight percent of the trisodium salt of e ad ed. The finished soapmixture subsequently is compound 7: solidified in cooling molds or oncooling plates.

ll (Fens i Example 4 HO-PC-POH (7) 70 m 011 air A storage-stable softammonium soap is obtained by The resuus f these tests are the sameregardless of stirring 0.5 percent of the dipotassium salt of Formula 2Whether the free acids or the alkali metal or ethanolamine compound,dissolved in l equal amount y g salts are used. The salts are obtainedfrom the free acids Water, iHtO the approximately 49 P t ap Paste.

by neutralization with the appropriate quantities of hy- 5 The soap thenis cooled in the usual manner.

Example 5 A storage-stable soft potassium soap is obtained by stirring0.5 percent of the Formula 2 compound (free acid), dissolved in an equalamount (by Weight) Water, into the hot, approximately 40 percent soappaste with 0.2 percent free alkali, calculated as KOH. The soap then iscooled in the usual manner.

We claim as our invention:

1. A surface-active material stabilized against rancidity anddiscoloration consisting of a Water-soluble compound selected from thegroup consisting of sodium-, potassiumand ammonium soaps or mixturesthereof and 6.05 to 2.5 weight percent of a stabilizer selected from thegroup consisting of a compound of the formula 0 R 0 HO-( 3-i OH Ht) 6H611 its sodium-, potassium, ammonium-, mono-, diand triethanolaminesalts, wherein R is a saturated aliphatic hydrocarbon having 1 to 11carbon atoms.

its sodium-, potasium, ammonium-, mono-, diand triethanolamine salts,wherein R is phenyl.

No references cited.

MURRAY KATZ, Primary Examiner.

LEON D. ROSDOL, Examiner.

B. BETTIS, Assistant Examiner.

